168023-81-2Relevant academic research and scientific papers
Stabilization of 16-electron paramagnetic organoiron species versus coordination of dinitrogen. X-ray crystal structures of [Fe(η5-C5H5)(N 2)(dippe)][BPh4], [Fe(η5-C5Me5)(dippe)][BPh4], and [Fe(η5-C5H5)Cl(dippe)][BPh4 ...
De La Jara Leal, Auxiliadora,Tenorio, Manuel Jiménez,Puerta, M. Carmen,Valerga, Pedro
, p. 3839 - 3847 (2008/10/09)
Full title: Stabilization of 16-electron paramagnetic organoiron species versus coordination of dinitrogen. X-ray crystal structures of [Fe(η5-C5H5)(N 2)(dippe)][BPh4], [Fe(η5-C5Me5)(dippe)][BPh4], and [Fe(η5-C5H5)Cl(dippe)][BPh4] (dippe = 1,2-bis(diisopropylphosphino)ethane). The purple compound [CpFeCl(dippe)] (Cp = C5H5; dippe = 1,2-bis(diisopropylphosphino)-ethane) reacts with dinitrogen and Na[BPh4] in EtOH or MeOH, to furnish the novel half-sandwich end-on dinitrogen complex [CpFe(N2)(dippe)][BPh4] (1). This compound is diamagnetic and dissociates dinitrogen reversibly in thf or acetone solution, to yield the paramagnetic complex [CpFe(dippe)][BPh4] (2). 1 and 2 are in equilibrium in acetone solution under dinitrogen. Thermodynamic parameters for such equilibrium have been estimated. The related complex [Cp*FeCl(dippe)] (Cp* = C5Me5) dissolves in MeOH or EtOH to yield only [Cp*Fe(dippe)]+, and no dinitrogen uptake is observed. The X-ray crystal structure of [Cp*Fe(dippe)][BPh4] (3) has been determined. The complexes 1-3 react with a variety of neutral donors L (L = CNBut, CO, MeCN) furnishing the corresponding adducts [CpFe(L)-(dippe)][BPh4] or [Cp*Fe(L)(dippe)][BPh4], as expected. The insertion of SnCl2 into the Fe-Cl bond only occurs in [FeCpCl(dippe)], yielding [CpFe(SnCl3)(dippe)]. Both [CpFeCl(dippe)] and [Cp*FeCl(dippe)] are readily oxidized by atmospheric oxygen in alcoholic solution to the corresponding FeIII derivatives, [CpFeCl(dippe)]+ and [Cp*FeCl(dippe)]+, respectively. The X-ray crystal structure has been determined for [CpFeCl(dippe)][BPh4].
